Engineering Commons^™

Hydrodeoxygenation Of Biomass Derived Sugar Alcohols To Platform Chemicals Using Heterogeneous Catalysts, Blake Macqueen

Theses and Dissertations

This work set out to investigate biomass derived sugar alcohol upgrading via the removal of oxygen and hydroxyl groups via the hydrodeoxygenation reaction utilizing heterogeneous catalysts. The importance of reaction conditions, catalyst meal loadings, catalyst structure and properties were probed using techniques such as design of experiments, and spectroscopic techniques including Raman and DRIFTS. The state of the art simultaneous hydrodeoxygenation (S-HDO) catalyst ReO_x-Pd/CeO₂ was investigated and optimized for various sugar alcohol substrates. The kinetics and associated mass transfer were also investigated to give further insight into the reaction over the ReO_xPd/CeO₂ catalyst.

First, …

Kinetics Study Of The Hydrodeoxygenation Of Xylitol Over A ReoX-Pd/Ceo2 Catalyst, Blake Macqueen, Michael Royko, Bradie S. Crandall, Andreas Heyden, Yomaira J. Pagán-Torres, Jochen A. Lauterbach

Faculty Publications

In this study, we elucidate the reaction kinetics for the simultaneous hydrodeoxygenation of xylitol to 1,2-dideoxypentitol and 1,2,5-pentanetriol over a ReOx-Pd/CeO2 (2.0 weight% Re, 0.30 weight% Pd) catalyst. The reaction was determined to be a zero-order reaction with respect to xylitol. The activation energy was elucidated through an Arrhenius relationship as well as non-Arrhenius kinetics. The Arrhenius relationship was investigated at 150–170◦ C and a constant H2 pressure of 10 bar resulting in an activation energy of 48.7 ± 10.5 kJ/mol. The investigation of non-Arrhenius kinetics was conducted at 120–170◦ C and a sub-Arrhenius relation was elucidated with activation energy …

Kinetics Study Of The Hydrodeoxygenation Of Xylitol Over A ReoX-Pd/Ceo2 Catalyst, Blake Macqueen, Michael Royko, Bradie S. Crandall, Andreas Heyden, Yomaira J. Pagán-Torres, Jochen A. Lauterbach

Faculty Publications

In this study, we elucidate the reaction kinetics for the simultaneous hydrodeoxygenation of xylitol to 1,2-dideoxypentitol and 1,2,5-pentanetriol over a ReOx-Pd/CeO2 (2.0 weight% Re, 0.30 weight% Pd) catalyst. The reaction was determined to be a zero-order reaction with respect to xylitol. The activation energy was elucidated through an Arrhenius relationship as well as non-Arrhenius kinetics. The Arrhenius relationship was investigated at 150–170◦ C and a constant H2 pressure of 10 bar resulting in an activation energy of 48.7 ± 10.5 kJ/mol. The investigation of non-Arrhenius kinetics was conducted at 120–170◦ C and a sub-Arrhenius relation was elucidated with activation energy …

Understanding Biomass Upgrading Through Hydrogenolysis Reactions: Kinetics And Mechanism, Jalal Tavana

Electronic Theses and Dissertations

This dissertation involves several hydrogenolysis reactions but is mainly focused on hydrodechlorination (HDC) of chlorobenzene (PhCl) and hydrodeoxygenation (HDO) of 2-furancarboxylic acid (FCA). Hydrodechlorination of PhCl has been the subject of research for some time. Here, we used a Pd/C catalyst to study this reaction though rigorous kinetics and mechanistic analyses in a CSTR reactor. The H₂/D₂ kinetic isotope effect (KIE) experiment revealed that H₂ is not involved in a rate controlling step. The kinetics data are in agreement with similar systems reported before and follow a first-order dependence on chlorobenzene, half order for hydrogen and …

Theoretical Investigation Of The Biomass Conversion On Transition Metal Surfaces Based On Density Functional Theory Calculations And Machine Learning, Wenqiang Yang

Theses and Dissertations

During the past decades, heterogenous catalyzed conversion of biomass to hydrocarbons with similar or identical properties to conventional fossil fuels has gained significantly academic and industrial interest. However, the conventional heterogeneous catalysts such as sulfided NiMo/Al₂O₃ and CoMo/Al₂O₃ used have various drawbacks, such as short catalyst lifetime and high sulfur content of product. To overcome the limitations of the conventional sulfided catalysts, new catalysts must be developed, which requires a better understanding of the reaction mechanism of the biomass conversion. Based on density functional theory, in this thesis, we reported a computational calculation study …

Carboxylic Acid Hydrodeoxygenation Over Supported Noble Metal Catalysts, Joshua Gopeesingh

Dissertations - ALL

Carboxylic acid hydrodeoxygenation (HDO) over supported noble metal catalysts was carried out in order identify the main challenges associated with supported monometallic catalysts and identifying solutions that may increase the practicality of these high activity metals. Using propionic acid as a probe molecule, it was found that supported platinum (Pt) and ruthenium (Ru) catalysts have two main issues: selectivity and stability. Both metals are quite unselective towards HDO products, multiple chemistries occur over the catalysts that lead to a myriad of undesired products. Decarbonylation (DCN) is the most selective pathway over Pt catalysts, while both DCN and methanation chemistries are …

Liquid Phase Modeling In Heterogeneous Catalysis, Mohammad Shamsus Saleheen

Theses and Dissertations

Conversion of lignocellulosic biomass into transportation fuels or commodity and specialty chemicals will be an important and fast-growing industry within the United States over the coming decades. Its growth will be driven by a variety of factors, including increased energy demands, environmental considerations, national security, and government mandates. To achieve the desired energy efficiency and economic impact, the emerging biorefining industries need novel heterogeneous catalysts with exceptional activity, selectivity, and stability. Catalytic materials developed in the petrochemical industries are generally not suitable for processing highly functionalized feedstocks typical of the biorefinery landscape. Due to the characteristics of this biomass feedstock …

Hydrodeoxygenation Of Pinyon-Juniper Catalytic Pyrolysis Oil, Hossein Jahromi

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Catalytic hydrodeoxygenation (HDO), is an effective process to convert oxygenated compounds to hydrocarbons. This process is widely used for improving the negative properties of biomass-derived pyrolysis oils (bio-oils) such as high acidity, poor stability, and low heating value. During this process oxygen is removed from the bio-oil in the form of water, thus the liquid product of HDO process consists of aqueous phase and hydrocarbon phase that can be easily separated. Synthesis of efficient HDO catalyst has been a major challenge in the field of bio-oil upgrading. Red mud, which is an alkaline waste from alumina industry was used to …

Heterogeneous Catalysis For The Upgrading Of Biomass Derived Chemicals Via Hydrodeoxygenation, Elizabeth Barrow

Theses and Dissertations

An important step in the upgrading of biomass derived chemicals is the removal of excess oxygen. The works reported here are focused on studying the heterogeneous catalysts that can be utilized for that upgrading through hydrodeoxygenation. This work begins with a discussion of the alkylation of short chain platform chemicals for chain growth and also demonstrates the proof of concept of combining alkylation and hydrodeoxygenation in a single step. Then, because of the promising nature of ReOx- Pd/CeO2 for selective hydrodeoxygenation, a detailed study of ReOx/CeO2 is presented. Finally, a new surface structure interpretation is presented for P/Ni(111) which could …

Economic Feasibility Of A Gasoline Production Plant From Lignocellulosic Feedstocks, Weixiang Guan, Sim-Ying Chua, Chi-Wing Tsang, Xiao Chen, Carol Sze Ki Lin, Raymond Sze Wai Fu, Haoquan Hu, Changhai Liang

Faculty of Science & Technology (THEi)

In this study, the conceptual process flowsheet was developed and the economic feasibility of woody biomass conversion to biofuel as feedstock was analysed by considering several promising experimental processes for lignin depolymerization, such as hydrodeoxygenation and hydrogenolysis, along with lignocellulosic biomass fractionation processes. The engineering simulation process toward the commercial production of bio-gasoline from lignocellulosic biomass using SuperPro Designer® was modeled. The compatibility of the end products with the current gasoline specifications was evaluated and various blending options were investigated to meet the octane number and Reid vapor pressure requirement of the product. The economic potential of the simulated engineering …

Nimoal Catalysts Derived From Heptamolybdate-Intercalated Layered Double Hydroxides For Hydrodeoxygenation Of Anisole, Chuang Li, Xingzhao Zhang, Xiao Chen, Zhijian Peng, Chi-Wing Tsang, Changhai Liang

Faculty of Science & Technology (THEi)

The catalytic performance of NiMoAl catalysts derived from layered double hydroxide (LDH) precursors with molybdenum species incorporated into the interlayers was investigated for the hydrodeoxygenation (HDO) of anisole as a model compound of the lignin. The results showed that high dispersion of small Ni nanoparticles with 2–5 nm due to the pinning effect of Mo from Mo7O246− intercalated the LDHs. Due to presence of the oxygen vacancy sites on the molybdenum oxide, the NiMoAl catalysts exhibit higher conversion of anisole than the corresponding NiAl catalyst. The activity for hydrodeoxygenation was enhanced with the increased content of molybdenum species, which can …

Nb(Ta)-Based Solid Acid Modified Pt/Cnts Catalysts For Hydrodeoxygenation Of Lignin-Derived Compounds, Weixiang Guan, Xiao Chen, Chuang Li, Jie Zhang, Chi-Wing Tsang, Haoquan Hu, Shaojie Li, Changhai Liang

Faculty of Science & Technology (THEi)

Efficient upgrading of lignin bio-oils into oxygen-free liquid alkane fuels is a challenging task owing to the incompatibility of the phenolic feedstock with conventional fuels and the availability of effective hydrotreating catalysts based on the current refinery infrastructure. In this work, a series of solid acid nanosheets (HNbWO6, HNbMoO6, HTaWO6) modified Pt/CNTs bifunctional catalysts were evaluated in hydrodeoxygenation (HDO) of lignin-derived compounds. The effects of types of nanosheets and the synergistic effect between metal sites and acid sites were discussed via HDO of diphenyl ether. Pt/HNbWO6/CNTs catalyst exhibited the most efficient performance for the HDO of diphenyl ether to cyclohexane …

Hydrodeoxygenation Of Aqueous Phase Catalytic Pyrolysis Oil To Liquid Hydrocarbons Using Multi-Functional Nickel Catalyst, Hossein Jahromi, Foster A. Agblevor

Biological Engineering Faculty Publications

Herein we investigated the hydrodeoxygenation (HDO) of aqueous phase pinyon-juniper catalytic pyrolysis oil (APPJCPO) using a new multifunctional red mud-supported nickel (Ni/RM) catalyst. The organic liquid yield after HDO of APPJCPO using 30 wt. % Ni/RM at reaction temperature of 350 °C was 47.8 wt. % with oxygen content of 1.14 wt. %. The organic liquid fraction consisted of aliphatics, aromatics, and alkylated aromatic hydrocarbons as well as small amounts of oxygenates. The RM support catalyzed ketonization of carboxylic acids. The Ni metal catalyzed partial reduction of oxygenates that underwent carbonyl alkylation with aldehydes and ketones on the RM. Catalyst …

Biomass-Derived Renewable Energy: Prospective Pathways And Key Barriers To Advanced Bio-Fuels, Mohammad Sadra Sharifi

Civil and Environmental Engineering Student Research

This paper provides a short review on recent advances in production of renewable energy through thermochemical processes followed by upgrading techniques such as hydrodeoxygenation, esterification, and steam reforming. Pyrolysis, gasification, and hydrothermal liquefaction have been the main processes of interest for the production of biomass energy for the past decades. However several challenges such as high capital cost due to high energy utilization for thermal processes and hydrogen consumption make these processes less competitive with the existing fossil fuel energy. Further processing of the raw bio-oil is required to improve its fuel properties such as energy density, octane number, and …

Hydrotreating Of Guaiacol: A Comparative Study Of Red Mud-Supported Nickel And Commercial Ni/Sio2-Al2o3 Catalysts, Hossein Jahromi, Foster Agblevor

Biological Engineering Faculty Publications

Upgrading of bio-oil through catalytic hydrotreating was investigated with guaiacol as a model compound. A nickel supported on red mud (Ni/RM) hydrotreating catalyst was developed and compared to the standard Ni/SiO₂-Al₂O₃ catalysts under similar experimental conditions. The Ni/RM catalyst was characterized by inductively coupled plasma atomic emission spectrometry (ICP-AES), X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), BET specific surface area, and temperature programmed reduction (TPR). The effects of reaction temperature (300, 350, 400 °C) and initial hydrogen pressure (4.83 MPa (700 psi), 5.52 MPa (800 psi), and 6.21 MPa (900 psi)) on products distribution …

Hydrodeoxygenation Of Acetic Acid Using Monometallic And Bimetallic Catalysts Supported On Carbon, José Luis Contreras Mora

Theses and Dissertations

Heterogeneous catalytic hydrodeoxygenation (HDO) of biomass-derived feeds is a deoxygenation process that is of highly interest. Carboxylic acids are one of the main components of bio-oils and acetic acid is one of the most abundant of these carboxylic acids. This acid is rich in oxygen, therefore a lot of research to produce fuel and other valuable chemicals such as ethanol is of interest.

This dissertation explores the gas-phase catalytic HDO of AA over catalysts supported on activated carbon (Cp-97). Temperature-dependent conversion and selectivity were studied at 1 atm from 200-400⁰C with an AA concentration of 1.1% and 20% …

Production Of Bio-Oil With Different Oxygen Content And Characterization Of Catalytic Upgrading To Transportation Fuel, Mubarak Mohammed Khlewee

Electronic Theses and Dissertations

The world’s increasing population requires an increase in transportation fuel production. The lack of production of transportation fuels due to the shortage of fossil fuel resources combined with concerns about global emissions of carbon dioxide from fossil fuel combustion are the two major issues that have driven researchers to actively pursue alternative sources for oil production. Biomass is being considered as an alternative feedstock to produce fuel and chemicals due to its abundance and renewability. It has many features that make it suitable as a source of transportation fuel production. However, the bio-oil produced by the fast pyrolysis process has …

Kinetics Of Glycerol Conversion To Hydrocarbon Fuels Over Pd/H-Zsm-5 Catalyst, Yang Xiao, Arvind Varma

Yang Xiao

Theoretical Investigation Of The Catalytic Hydrodeoxygenation Of Levulinic Acid Over Ru (0001) Catalyst Surface, Osman Mamun

Theses and Dissertations

Due to the rapidly declining fossil fuel reserves and the onset of global climate change, the development of active, selective, and stable catalytic materials for the efficient production of biomass derived platform chemicals, i.e., levulinic acid (LA), succinic acid (SA), γ-valerolactone (GVL) etc., is receiving considerable attention in order to produce second generation biofuels and commodity chemicals. Though solid lignocellulosic biomass is significantly cheaper than petroleum; however, the available technology is the significant barrier for large scale utilization of biomass for the production of biofuels. The development of biomass conversion technology requires, 1) identification of potential biomass chemicals that can …

Development Of Heterogeneous Catalysts For Upgrading Biomass Pyrolysis Bio-Oils Into Advanced Biofuels, Shouyun Cheng

Electronic Theses and Dissertations

The massive consumption of fossil fuels and associated environmental issues result in an increased interest in alternative resources such as biofuels. The renewable biofuels can be upgraded from bio-oils that are derived from biomass pyrolysis. Catalytic cracking and hydrodeoxygenation (HDO) are two most promising bio-oil upgrading techniques for biofuel production. Heterogeneous catalysts are essential for upgrading bio-oil into hydrocarbon biofuel. Although some progresses have been made, the cost and effectiveness of catalysts still remain challenges. The main objective of this study was to develop efficient heterogeneous catalysts for upgrading bio-oils into advanced hydrocarbon biofuel with low costs. In catalytic cracking, …

Hydrodeoxygenation Of Pinyon Juniper Catalytic Pyrolysis Oil To Hydrocarbon Fuels, Hossein Jahromi, Foster Agblevor

Biological Engineering Faculty Publications

As a renewable source, biomass is an essential option for diminishing dependence on conventional fossil fuel energy sources. Pyrolysis is a promising technology for the conversion of biomass into liquid fuels. However, several challenges associated with using pyrolysis oils such as their high acidity and low energy content inhibit their direct use as transportation fuels. We conducted a batch hydrodeoxygenation of pinyon juniper catalytic pyrolysis oil using Ni/SiO2-Al2O3 catalyst to improve the following properties of the oil: heating value, acidity, oxygen content, water content, and viscosity. During the hydrogenation process, the influence of four experimental factors; temperature, catalyst loading, residence …

Conversion Of Glycerol To Hydrocarbon Fuels Via Bifunctional Catalysts, Yang Xiao, Arvind Varma

Yang Xiao

Hydrodeoxygenation Of Guaiacol Over Ni@Pd And Ni@Pt Bimetallic Overlayer Catalysts.Pdf, Qinghua Lai

Qinghua Lai

Biomass Catalytic Upconversion With A Metallic Catalyst Bed Under Radio Frequency Induction Heating, Mohammad Abu-Laban

LSU Master's Theses

This study investigated the thermal performances of platinum particles when coupled on a steel support, under the application of a radio frequency (RF) field. Platinum nanoparticles were reduced on the surfaces of type-316 stainless steel balls, based on published methods of Pt reduction from chloroplatinic acid. Alternatively, 1wt. % Pt/Al2O3 commercial catalyst pellets were mixed with stainless steel balls and investigated for hydro-deoxygenation of pyrolysis oil from pine sawdust biomass. The catalysts were placed inside an electric insulator tube suspended within a looping copper coil connected to the induction heater, and heated at different power levels. An infrared camera was …

Novel Carbon-Supported Transition Metal Phosphide Catalysts For Hydrodeoxygenation Of Fast Pyrolysis Oil, Cheng Guo

Electronic Thesis and Dissertation Repository

Catalytic hydrodeoxygenation (HDO) is considered to be the most promising route to upgrade pyrolysis oil to liquid transportation fuels. The objective of this research was to explore inexpensive supported metal oxides/metal phosphide catalysts for the upgrading of pyrolysis oil into advanced drop-in hydrocarbon liquid fuels by HDO.

The first stage of this thesis project investigates a series of molybdenum oxides/phosphide catalysts on different supports that were prepared in-house, such as Al₂O₃, activated carbon (AC), MgAl₂O₄ and Mg₆Al₂(CO₃)(OH)₁₆. The HDO activity of these catalysts were investigated …

Activated Carbon, Carbon Nanofiber And Carbon Nanotube Supported Molybdenum Carbide Catalysts For The Hydrodeoxygenation Of Guaiacol, Eduardo Santillan-Jimenez, Maxime Perdu, Robert Pace, Tonya Morgan, Mark Crocker

Center for Applied Energy Research Faculty and Staff Publications

Molybdenum carbide was supported on three types of carbon support—activated carbon; multi-walled carbon nanotubes; and carbon nanofibers—using ammonium molybdate and molybdic acid as Mo precursors. The use of activated carbon as support afforded an X-ray amorphous Mo phase, whereas crystalline molybdenum carbide phases were obtained on carbon nanofibers and, in some cases, on carbon nanotubes. When the resulting catalysts were tested in the hydrodeoxygenation (HDO) of guaiacol in dodecane, catechol and phenol were obtained as the main products, although in some instances significant amounts of cyclohexane were produced. The observation of catechol in all reaction mixtures suggests that guaiacol was …

Gas-Phase, Catalytic Hydrodeoxygenation Of Propanoic Acid Over Supported Group Viii Noble Metals, Yuliana K. Lugo José

Theses and Dissertations

Recent advances for the deoxygenation of biomass, have demonstrated that hydrodeoxygenation (HDO) is one of the most promising route for the upgrading pyrolysis bio-oils. Catalytic hydrodeoxygenation of pyrolysis bio-oil have shown to be an efficient and economical process, since the raw materials consist mainly of waste. Propanoic Acid (PAc) is considered as one of the main constituents of pyrolysis bio-oils. However, these carboxylic acids are extremely corrosive and difficult to deoxygenate. Therefore, much effort have been given to the development of novel catalytic techniques, to improve the activity, stability and selectivity for the HDO of carboxylic acids.

This dissertation explores …

Lab-Scale Fast-Hydropyrolysis And Vapor-Phase Catalytic Hydrodeoxygenation For Producing Liquid Fuel Range Hydrocarbons From Intact Biomass, Vinod Kumar Venkatakrishnan

Open Access Dissertations

Liquid transportation fuels are primarily produced from petroleum-based non-renewable carbon sources. Sustainably available lignocellulosic biomass, as a renewable form of atmospheric carbon, could be utilized to produce hydrocarbon-based fuels with high energy density. One of the process options for this conversion is the H2Bioil process, where biomass is rapidly heated in a hydrogen environment to produce fast-hydropyrolysis vapors that are catalytically upgraded in downstream hydrodeoxygenation (HDO) to produce hydrocarbons. This process has been modeled to have high carbon and energy efficiencies of ~70% and ~75%, respectively.

This dissertation presents the results of a lab-scale experimental proof-of-concept for the H2Bioil process …

High-Pressure Vapor-Phase Catalytic Hydrodeoxygenation Of Lignin-Derived Compounds To Hydrocarbons On Bimetallic Catalysts In The Range Of 0.2-2.4 Mpa., Sara Lynn Yohe

Open Access Dissertations

Biomass, as the only renewable source of carbon, presents a sustainable alternative to liquid fossil fuels for the production of renewable transportation fuels and chemicals. The lignin portion of biomass poses a significant challenge in the upgrading and conversion of lignocellulosic biomass to fuels and chemicals, and in many current biorefineries is not utilized. However, the lignin fraction is a valuable feedstock due to its aromatic structure, lower O:C ratio than cellulose and hemicellulose, and high energy content (up to 40%) and weight fraction (average 25 wt%) of biomass. Several processes (including fast-pyrolysis, fast-hydropyrolysis, and liquid phase processing) are able …

Upgrading Pyrolysis Oil To Produce Liquid Transportation Fuels, Ehsan Reyhanitash

Electronic Thesis and Dissertation Repository

The effects of stabilizing fast pyrolysis oil via catalytic alcohol pretreatment on upgrading via hydrodeoxygenation or thermal treatment was studied by comparing the properties of upgraded-stabilized oils with those of upgraded-non-stabilized oils (benchmarks). The major expected effect was reduction in molar mass of upgraded oils, as stabilization was expected to reduce the reactivity of fast pyrolysis oil, thereby reducing polymerization. It was observed that molar mass reduction was induced by dilution effect of the alcohol rather than reactivity reduction due to stabilization. Also, the effects of different alcohols on stabilization and subsequent upgrading were examined at minimized dilution effect conditions. …